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Advanced Oxidation Treatment of Drinking Water: Part I. Occurrence andRemoval of Pharmaceuticals and Endocrine-Disrupting Compounds fromLake Huron WaterMohammad Feisal Rahmana; Earnest K. Yanfula; Saad Y. Jasimab; Leslie M. Braggc; Mark R. Servosc;Souleymane Ndiongueb; Devendra Borikarb

a Department of Civil and Environmental Engineering, The University of Western Ontario, London,Ontario, Canada b Walkerton Clean Water Centre, Walkerton, Ontario, Canada c Department ofBiology, The University of Waterloo, Waterloo, Ontario, Canada

Online publication date: 30 July 2010

To cite this Article Rahman, Mohammad Feisal , Yanful, Earnest K. , Jasim, Saad Y. , Bragg, Leslie M. , Servos, Mark R. ,Ndiongue, Souleymane and Borikar, Devendra(2010) 'Advanced Oxidation Treatment of Drinking Water: Part I.Occurrence and Removal of Pharmaceuticals and Endocrine-Disrupting Compounds from Lake Huron Water', Ozone:Science & Engineering, 32: 4, 217 — 229To link to this Article: DOI: 10.1080/01919512.2010.489185URL: http://dx.doi.org/10.1080/01919512.2010.489185

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Ozone: Science & Engineering, 32: 217–229

Copyright # 2010 International Ozone Association

ISSN: 0191-9512 print / 1547-6545 online

DOI: 10.1080/01919512.2010.489185

Advanced Oxidation Treatment of Drinking Water: Part I.Occurrence and Removal of Pharmaceuticals and Endocrine-Disrupting Compounds from Lake Huron Water

Mohammad Feisal Rahman,1 Earnest K. Yanful,1 Saad Y. Jasim,1,2 Leslie M. Bragg,3

Mark R. Servos,3 Souleymane Ndiongue,2 and Devendra Borikar2

1Department of Civil and Environmental Engineering, The University of Western Ontario, London, Ontario, Canada2Walkerton Clean Water Centre, Walkerton, Ontario, Canada, N0G 2V03Department of Biology, The University of Waterloo, Waterloo, Ontario, Canada

The current study focuses on the occurrence of selectedendocrine disrupting compounds, pharmaceuticals and perso-nal care products in Lake Huron Water and their removalusing ozone/hydrogen peroxide based pre-coagulation,advanced oxidation process (AOP). Raw Lake Huronwater spiked with nine target compounds was treated in adual train pilot scale treatment plant. None of the targetchemicals showed any significant removals following conven-tional treatment processes (coagulation, sedimentation andfiltration). Five of the nine target pollutants plummeted toconcentrations below the method detection limits followingAOP. For all the target compounds AOP treatment providedhigher removal compared to conventional treatment.

Keywords Ozone, Advanced Oxidation Process, Lake Huron,Pharmaceuticals, Endocrine-Disrupting Com-pounds, Drinking Water

INTRODUCTION

Increased interest in the fate of endocrine-disruptingcompounds (EDCs) and pharmaceuticals and personalcare products (PPCPs) in the environment has been trig-gered by the discovery of trace concentrations (ng/L tomg/L) of these compounds globally in the aquatic envir-onment (Halling-Sorensen et al., 1998; Ternes et al., 1998;Stumpf et al., 1999; Kolpin et al., 2002; Metcalfe et al.,2003a,b; Boyd et al., 2003; Metcalfe et al., 2004;Stackelberg et al., 2004; Jones et al., 2005; Jasim et al.,

2006; Stackelberg et al., 2007; Kim et al., 2007; Vienoet al., 2007; Barnes et al., 2008; Peng et al., 2008). EDCsand PPCPs include products that are used in large quan-tities in everyday life such as human and veterinary drugs,surfactants and industrial chemicals (Petrovic et al.,2003). They are released into aquatic environmentsmainly via sewage treatment plant effluents and agricul-tural runoff. Since conventional sewage treatment pro-cesses fail to eliminate them efficiently, they end up innatural waters. Figure 1 shows various routes of entry ofthese chemicals into water and their circulation in theaquatic environment (adapted from Petrovic et al.,2003). Despite high transformation and removal rates,many EDCs and PPCPs are persistent in the environmentdue to their continuous release (Jasim et al., 2006).

Adverse impacts of this diverse group of chemicalshave been documented for wildlife including increasedfeminization of fish, sexual disorders in snails and juve-nile alligators, and kidney failure in vultures leading todeath (Guillette et al., 1994; Purdom et al., 1994;Lintelmann et al., 2003; Kavanagh et al., 2004; Profittand Bagla 2004; Orlando et al., 2007; Rahman et al.,2009). The issue of possible human health impacts gar-nered considerable concern after it was confirmed thatEDCs and PPCPs are capable of causing hormonal dis-ruption in wildlife. Many of these chemicals have thepotential to generate biological responses within thehuman body as they are designed that way.

Scientists have often linked occurrences of these che-micals in the environment to increased incidences of hor-monal cancers, early puberty in girls, suppressed pubertyin boys, inhibited neurological development in infants,decline in sperm quality and quantity in men, and

Received 9/22/2009; Accepted 3/10/2010Address correspondence to E.K. Yanful, Department of Civil

and Environmental Engineering, The University of WesternOntario, 1151 Richmond Street, London, Ontario, Canada.E-mail: [email protected]

Advanced Oxidation for Drinking Water Treatment- Lake Huron: Part I July–August 2010 217

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declining sex ratio (Colon et al., 2000; Pocar et al., 2003;Sharpe and Irvine 2004; Sumpter 2005). However, theseclaims have been refuted by many authors (Hemminkiet al., 1998; Marcus et al., 1998; Safe 2000). Thus, whilethe scientific community remains divided over the issue ofimpact on humans, it is certain that our understanding ofthese chemicals in the environment is limited.

Studies have shown that conventional water treatmentprocesses such as coagulation, flocculation, sedimentationand biological filtration remain largely ineffective in elim-inating these trace contaminants (Ternes et al., 2002;Westerhoff, 2003; Snyder et al., 2003; Stackelberg et al.,2004; Westerhoff et al., 2005; Mcdowell et al., 2005; Vienoet al., 2006, 2007; Stackelberg et al., 2007; Snyder et al.,2007). This could be attributed to their differing chemicalproperties, high water solubility and occurrence in traceconcentrations. Thus, there is a risk of indirect exposureto these chemicals via drinking water (Huber et al., 2003;Mcdowell et al., 2005). Regardless of the fact that negativeimpacts on human health remains debated, from a generalprecautionary principle it should be ensured that the leastnumber of anthropogenic chemicals be present in drinkingwater (Ternes et al., 2002; Mcdowell et al., 2005). Also,there is mounting pressure on the drinking water industryto eliminate these chemicals from water as public and reg-ulatory bodies become more informed of the issue.

In the present study, the occurrence and removal of 9EDCs and PPCPs belonging to different functionalgroups and listed in Table 1 were studied using LakeHuron water. The compounds are atrazine, an extensivelyused pesticide, bisphenol-A (BPA), a plasticizer that hasrecently been banned from use in infant bottles inCanada, diclofenac, ibuprofen and naproxen all widelyused analgesics, carbamazepine and fluoxetine both anti-depressants, and gemfibrozil and atorvastatin, lipid

regulators. Most of these compounds have been identifiedin raw and treated drinking water (Metcalfe et al., 2004;Stackelberg et al., 2004; Jones et al., 2005; Hua et al.,2006a, 2006b.; Jasim et al., 2006; Stackelberg et al., 2007).

Lake Huron is one of the primary sources of drinkingwater for many communities around the Great Lakesregion. Yet, it remains unexplored in terms of studies onEDCs and PPCPs contamination. Also, limited data isavailable on the elimination of EDCs and PPCPs fromLake Huron water during drinking water treatment. Pre-coagulation ozonation has earlier been reported to benefitsubsequent drinking water treatment processes andimprove finished water quality (Anderson et al., 1996;Paode et al., 1995; Jasim et al., 2008). It also minimizestrihalomethanes (THMs) precursors, and assists in tur-bidity and particles removal (Chang and Singer 1991;Anderson et al., 1996; Mazloum et al., 2004; Rakness2005; Jasim et al., 2008). Advanced oxidation process(AOP) involves the oxidation of target contaminants by�OH radicals (Rosenfeldt et al., 2006).

Ozone (O3) in combination with hydrogen peroxide(H2O2) can elevate the concentration of non-preferentialhydroxyl radicals (�OH) during ozonation, and lead toimproved elimination of ozone (O3) refractory compounds(Zweiner and Frimmel, 2000; Von Gunten, 2003; Snyderet al., 2006; Rakness, 2005). Thus, using pre-coagulationAOP would not only achieve effective removal of EDCsandPPCPs but would also yield secondary benefits in drink-ing water treatment. It is expected that, like many otherorganic compounds, AOP derived by-products of parentEDCs andPPCPswould bemore susceptible to biodegrada-tion (Von Gunten, 2003; Mcdowell et al., 2005; Rakness,2005).

The objective of the present study was to evaluate theefficiency of the pre-coagulation ozone/hydrogen peroxide

FIGURE 1. Chemicals contamination of aquatic environment through various environmental compartments (adapted from Petrovic et al.,2003). Darker lines indicate major routes of entry.

218 M.F. Rahman et al. July–August 2010


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(O3/H2O2) based AOP in removing the above mentionedtarget compounds from water. In addition, the study inves-tigated the effectiveness of different treatment steps duringpilot-scale drinking water treatment. The study also looked

into the occurrence of the target chemicals in Lake Huronwater. The experimental work was conducted at the pilot-scale treatment facility at the Walkerton Clean WaterCentre (Centre), Walkerton, Ontario, Canada. Analysis of

TABLE 1. Selected Properties and Method Detection Limits for the Target Compounds

Compound (CAS #) Use/Therapeutic class MW log KOW MDL (ng/L) Structure

Atrazine (ATZ)(1912-24-9)

Herbicides 215.71 2.611 0.025

Bisphenol-A (BPA)(80-05-7)

Plasticizer 228.32 3.323 10

Carbamazepine(CBZ) (298-46-4)

Anti-depressant 236.11 2.451 0.05

Flouxetine (FLX)(54910-89-3)

Anti-depressant 309.11 4.051 0.2

Diclofenac (DIC)(15307-86-5)

Analgesics 294.01 0.701 0.15

Ibuprofen (IBU)(15687-27-1)

Analgesics 206.31 3.971 1

Naproxen (NAP)(22204-53-1)

Analgesics 230.11 3.181 0.2

Gemfibrozil (GEM)(25812-30-0)

Lipid Regulator 250.41 4.771 0.15

Atorvastatin (ATV)(134523-00-5)

Lipid Regulator 558.72 6.362 1

1. Snyder et al.(2007); 2. http://www.srcinc.com/what-we-do/databaseforms.aspx?id=385; 3. Stackelberg et al. (2007); CAS # – Chemical Abstracts

Service Number; MW - Molecular Weight; log KOW - Octanol Water Partition Coefficient; MDL- Method Detection Limit.



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grab samples for detection of the target EDCs and PPCPswere performed at the Waterloo Aquatic Toxicology andEcosystem Remediation Laboratory, University ofWaterloo, Waterloo, Ontario, Canada.

EXPERIMENTAL WORK

Raw Water

Raw water, collected from a drinking water treatmentplant intake on Lake Huron, Ontario, Canada (Figure 2),was taken to the pilot plant a day before the start of each runand was stored in three above-ground tanks. Experimentswere conducted between April 2008 and October 2008.Measured water quality parameters at the time of samplingare presented in Table 2. Alkalinity and total hardness mea-sured on the raw water were in the range of 80–106 mg/L asCaCO3 and 91–117mg/L as CaCO3, respectively. Dissolvedorganic carbon (DOC) concentrations in the rawwater werefairly low (1.2–1.9 mg/L). However, turbidity varied widely(1.16–73.8 NTU). High turbidity was encountered on twooccasions following storm events.

Reagents and Chemicals

Table 1 identifies theEDCsandPPCPs thatwere studied.The raw water was spiked with these compounds simulta-neously at pre-determined concentrations. Bisphenol A,diclofenac, carbamazepine, gemfibrozil, and naproxenwere obtained from Sigma-Aldrich (Oakville, ON,Canada) at the highest purity commercially available.Atrazine was obtained from Chem Service (West Chester,PA, USA), fluoxetine was purchased from Interchem(Paramus, New Jersey, USA), atorvastatin from SynFine(Richmond Hill, ON, Canada) and ibuprofen from TCIAmerica (Portland, OR, USA). High performance liquidchromatography (HPLC) grade methanol and water wereobtained from Fisher Scientific and tert-butyl methyl ether(MTBE) from Sigma-Aldrich (Oakville, ON, Canada).

FIGURE 2. Location of the raw water intake plant.

TA

BL

E2.

Raw

Wate

rQ

ualit

yand

Sele

cte

dT

reatm

ent

Para

mete

rsfo

rth

eP

ilot-

Scale

Experim

ents

Date

ofexperim

ent

22–23April2008

18–19June2008

19–20August

2008

26–27August

2008

01–02October

2008

08–09October

2008

Runno.

12

34

56

Raw

Water

pH

8.2

8.2

8.3

7.6

8.1

8.1

Turbidity(N

TU)

40.6

1.89

3.11

73.8

1.16

1.16

Alkalinity(m

g/L

asCaCO

3)

106.4

94.4

84

88

80

84

Hardness(m

g/L

asCaCO

3)

108.8

116.8

91.2

101.6

92.8

94.8

DOC

(mg/L)

1.7

1.9

1.7

1.7

1.5

1.8

UV254(cm

-1)

0.019

0.022

0.0209

0.0138

0.0121

0.0111

Tem

perature

(�C)

12.7

19.1

23

22.9

15.7

17.1

Treatm

entParameters

H2O

2Injection

H2O

2applied

priorto

Ozoneaddition

H2O

2after

Ozoneaddition

PACldose

66

610

63.7

O3Dose

(Train

2Only)

2.0–2.3

H2O

2Dose

(Train

2Only)

0.2



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Nano-purewaterwas producedusing aBarnsteadFiltrationSystem. Concentrated spiking solution was prepared inmethanol at a high concentration (1g/L). Stock solutionwas prepared a day before spiking and was stored at -20�C before use. Stock solution was transported in an amberglass vial in chilled conditions to the pilot plant.

SternPACTM polyaluminium chloride (PACl) (EagleBrook, Inc., Varennes, Quebec, Canada) was used as coagu-lant for coagulation treatment. Hydrogen peroxide (H2O2)(35%) was purchased from Canada Colors and ChemicalsLtd. Ozone gas was generated at the pilot plant using PacificSGC11 ozone generator (Pacific Ozone Technology,Benicia, CA, USA).

Pilot Plant Experiments

The pilot-scale treatment facility at the WalkertonClean Water Centre (Centre) is an automated dual traintreatment plant (Corix Water Systems, Langley, BC,Canada), which runs on gravity flow and can treat upto 15.0 L/min. Both treatment trains include identicalcoagulation, flocculation and dual media (sand andanthracite) filtration units (Figure 3). In Train 2, O3 andH2O2 may be added to the system either prior to or aftersedimentation. In the current study, however, only pre-coagulation AOP was performed.

Water flow rate, turbidity, pH, raw water temperatureand high concentration ozone gas input data are collectedusing online sensors, transmitters and supervisory controland data acquisition system (SCADA) (Appendix-A).Dakins Engineering Group of Mississauga, Ontario,Canada developed the SCADA system using iFix software(Supplied by GE Fanuc Canada, Mississauga, Ontario,Canada) (Jasim et al., 2008). The O3/H2O2 based AOP unitconsists of two serially connected identical glass columns(Column 1 and Column 2). Ozone gas is added only in thefirst column. Each column can contain about 40 liters of

water. Column 1 is considered as the mixing column andColumn 2 is considered as the main reactor. Feed water ispumped to the AOP system through the top inlet port of thefirst glass column. Water then flows by gravity throughoutthe system.

The first column is operated in downstream mode andthe second in upstream (Jasim et al., 2008). Hydrogenperoxide stock solution is pumped to the system using aMasterflex 7523-70 drive with 77250-62 pump head (ColePalmer, Vernon Hills, Illinois, USA). An ambient ozonegas monitor (GasSens) is employed to monitor ambientozone concentration. The ozone system off-gas afterbeing collected at the top of each column is transportedto a heated ozone destruction unit and finally released inthe air outside the building (Jasim et al., 2008).

The plant was operated at a total flow of 12.4 L/min. Anoverhead flow splitter divided the total flow and directedeach half (6.2 L/min) towards the treatment trains. Prior toreaching the flow splitter, the feed water was spiked withtarget EDCs and PPCPs stock solution using a Masterflex7523-70 drive with a 77250-62 pump head (Cole Palmer,VernonHills, Illinois, USA). After passing through floccu-lation chamber and clarifier, the water was filtered usingsand/anthracite dual media filter column (15 cm diameter).Filters were operated at filtration rate of 10 m/hr.Disinfection of filtered water was not performed duringthe study.

Experiments were conducted with the goal of achievinga target filtered water turbidity of less than 0.1 NTU andcoagulant doses were adjusted accordingly to obtain thetarget turbidity. SternPAC polyaluminum chloride (PACl)was used as coagulant for the agglomeration process. Acoagulant dose of 6 mg/L polyaluminum chloride (PACl)(Eagle Brook, Inc., Varennes, Quebec, Canada) was usedfor all runs except Run 4 and Run 6. Coagulant doses weredetermined using a programmable jar tester (Phipps &Bird 900). Since high turbidity was encountered during

FIGURE 3. Schematic of the pilot plant.



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Run 4 (following a heavy rainfall event), the coagulantdose was increased to 10 mg/L to achieve the target filteredwater turbidity. During Run 6 coagulant dose was reducedfrom 6 mg/L to 3.7 mg/L after almost 7 hours of operationto assess how the system performs below optimum coagu-lant dose.

Ozone gas was added to the water using a Mazzeiinjector (Bakersfield, CA, USA) and at a dose that rangedfrom 2.0–2.3 mg/L. H2O2 was infused at a concentrationof 0.2 mg/L. H2O2 during Run 1 through Run 3 wasinjected into the system upstream of ozone addition(pre-ozonation H2O2) and downstream of ozone (post-ozonation H2O2) during Run 4 through Run 6. Table 2lists the observed raw water characteristics and treatmentparameters used during the study.

Operation of the pilot plant started the morning afterraw water had been brought to the facility. Followingnecessary modification to operating conditions the plantwas allowed to run in stable conditions overnight. Grabsamples were collected the next morning. During the timebetween the arrival of raw water in the laboratory andbefore sampling, the water acclimatized to the laboratorytemperature. Also, raw water turbidity decreased slightlydue to settling of suspended particles during this timeperiod. No quenching chemicals were added as the onlinesensors did not show any residual ozone in AOP efflu-ents. H2O2 residuals were not expected to occur at the lowdose applied during this study. Urfer and Huck (1997)showed that H2O2 residuals, if present, would be con-sumed by subsequent biological filters in treatment train.

Sample Collection and Preservation

Grab samples were collected in 1 L I-ChemEnvironmental Sample Type III amber glass sample bot-tles (Fisher Scientific). Sample bottles were treated with 1g/L of sodium azide to avert microbial degradation and50 mg/L of ascorbic acid to quench any residual oxidant(Vanderford and Snyder, 2006). Finally, sample bottleswere placed in coolers with ice packs for transporting tothe pilot plant. For detection of EDCs and PPCPs, rawwater, spiked water, AOP treated water (Train 2 only),clarified water and filtered water samples were collectedfrom sampling taps of both treatment trains. Threereplications of each sample were collected for qualityassurance purpose. After collection, samples were againplaced in coolers and brought back to the laboratorywithin 5 hr of collection and refrigerated at 4�C.Samples were extracted within 5 days of collection.

Analytical Methods

Solid phase extraction (SPE) and liquid chromatography/tandemmass spectrometry (LC-MS/MS), using electrosprayionization (ESI) in both positive and negative modes wasused to analyze the target EDCs and PPCPs (Vanderfod andSnyder, 2006). The method described by Vanderford andSnyder (2006) was modified for the QTrap 3200 system

(Applied Biosystems/MDS Sciex, Concord, ON, Canada).EDCs and PPCPs were extracted from aqueous media usingSPE. Oasis hydrophilic-lipophilic balance (HLB) SPE car-tridges (6 mL, 500 mg, Waters Corporation, Millford, MA,USA) were preconditioned with 5 mL of MTBE, 5 ml ofmethanol and 5 ml of HPLC grade water at an approximateflow rate of 5 mL/min.

Before introducing collected grab samples to HLB car-tridges, each sample volume was brought down to 500 mLand spiked with 50 mL of 100 mg/L deuterated spiking stan-dards. Samples were then introduced at approximately 15mL/min and at a vacuumpressure less than 20mmHg.HLBcartridges were then rinsed with 5 mL of HPLC grade waterand allowed to drain under vacuum for about 15 minutes.For elution purposes, 5mLofmethanol followed by 5mLof10:90 (v/v) methanol/MTBE solutions were used. Elutedfractions were collected in test tubes and evaporated to dry-ness under a gentle streamofnitrogen.The extractswere thenbrought to a final volume of 500 mL using methanol(Vanderford and Snyder, 2006). Extracted samples werefinally placed into 2 mL amber glass vials, stored in labeledcryoboxes and placed in the freezer at -20 �C until analyzed.

SPE extracts were analyzed using an Agilent 1200series HPLC system (Agilent, Santa Clara, CA, USA)with a API 3200 Qtrap (triple quadrapole ion trap) tan-dem mass spectrometer with an electrospray ionization(ESI) TurboIon Spray source (Applied Biosystems MDSSciex, Concord, ON, Canada). The HPLC system con-sists of a degasser, autosampler, column oven and abinary pump. Analytes were separated on an AgilentEclipse XDB-C18 column (150 � 4.6 mm, 5 mm,Chromatographic Specialties Inc., Brockville, ON,Canada). For ESI positive and ESI negative analysis abinary gradient of 5 mM ammonium acetate in water(mobile phase A) and 100% methanol (mobile phase B)was used at a flow rate of 800 mL/min. The total run timesfor ESI positive and ESI negative analysis were 8.0 minand 11.0 min per sample, respectively.

For ESI positive analysis 60% B was held for 0.5 min,raised to 80% B at 0.51 min and then increased linearly to100% B at 5.0 min. B was held at 100% for 1 min andwas linearly brought down to 60% B at 6.5 min and thenheld at 60% B for 1.5 min. For ESI negative analysis 10%B was held for 0.5 min and was stepped to 60% B at 0.51min and then was linearly raised to 100% B at 8.0 minand held at 100% B for 0.5 min. The gradient wasbrought down to 10% B at 8.51 min and held at 10% Bfor 2.5 min. Analyst version 1.4.2 software was used fordata collection, analysis and control of components of theHPLC system (Applied Biosystems, Concord, ON,Canada). Selective specific masses as listed in Table 3were scanned with multiple reaction monitoring(MRM). Method detection limits (MDLs) for the targetcompounds are provided in Table 1. Optimization para-meters for the mass spectrometer are shown in Table 3and Table 4.



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Data Analysis and Assumptions

Target compounds concentrations are divided into 3categories as follows: not detected, detected belowmethod detection limits (MDLs) but could not be quan-tified reliably, and detected above MDLs. Each com-pound in a particular sample could fall into any of thesecategories. The sum of the number of samples of a targetcompound (A) in each of the above mentioned categoriesfor a particular sampling port (B) would indicate the totalnumber of samples analyzed for compound A for thesampling port B.

To calculate mean concentrations and mean removals avalue of zero was assigned when target compound concen-trations are either belowMDLs or not detected. Thus, 100%removal of a particular compound (A) in a particular sam-pling port (B) would indicate none of the analyzed samplesfor sampling port B had detectable concentration of com-pound A. When average concentration and percentageremovals for runs (Run 1 to Run 3) with pre-ozone H2O2

injection were compared with post-ozone H2O2 runs (Run 5

toRun6)no significant differenceswereobserved.Thus, datafor the study were analyzed considering a set of total 5 runs.

Detected concentration of all target compounds forRun 4(27 August, 2008) for all sampling ports, except for AOPeffluent were in line with concentrations observed duringthe other runs for respective sampling ports. Unlike theother runs, concentrations of target compounds in AOPeffluent samples collected during Run 4 were unduly higherthan spiked concentrations. Occurrence of such high concen-trations following AOP certainly triggered questions andaccordingly after considering different possibilities (such asanalytical method error, matrix effect, sampling error andturbidity) it was concluded that the data for AOP effluentfor Run 4 were not valid. The source of error however, couldnot be verified. Thus, to avoid any bias in data analysis, thedata set for the whole Run 4 was not considered during dataanalysis.Results ofRun 4 can be found atRahman (2008) forinterested readers.

RESULTS AND DISCUSSION

Occurrence in Raw Water

Of the 9 target compounds, atrazine, carbamazepine,fluoxetine were detected in at least 4 samples at averageconcentrations of 57 ng/L, 29 ng/L and 20 ng/L, respec-tively. Atorvastatin and ibuprofen were detected onlyonce. Thus 6 of the 9 target compounds were not detectedin at least 4 raw water samples. Figure 4 presents con-centrations of detected compounds in raw water. Atrazineis widely used around North America. In the US alone,nearly 3.3 � 107 kg of atrazine are used every year andapproximately 3.3 � 106 kg per annum are used in theGreat Lakes Basin during April to June primarily in cornfields (Hua et al., 2006a, 2006b). Atrazine was consis-tently detected in all raw water samples collected duringthe current study at an average concentration of 57 ng/L.

However, this observed mean concentration of occur-rence of atrazine in raw Lake Huron drinking water

TABLE 3. Compound-dependent Parameters

CompoundRetentiontime (min)

Precursorion(m/z)

Production(m/z)

Declusteringpotential (v)

Collisioncell exit potential (v)

Collisionenergy (ev)

Entrancepotential (v)

ESI NegativeIBU 5.95 204.9 160.9 -41 -19.237 -11 -2.6BPA 6.22 227 211.9 -53 -20.055 -28 -10NAP 4.62 229 170 -29 -20.129 -25 -1.9GEM 7.77 249.1 121.1 -55 -20.873 -17 -2DIC 5.51 293.9 250 -46 -22.53 -15 -2.5ESI PositiveATV 3.64 559.3 440.2 83 18.91 32 5.9ATZ 4.16 216.2 174.3 66.9 13.5 27 3.8CBZ 3.75 237.1 193.3 55 14.3 51 4.9FLX 6.37 310.3 44.3 48 12.08 44 2.9

TABLE 4. Source-dependent Parameters

ESI positive ESI negative

Collision gas (psig) 8 6Curtain gas (psig) 30 10Ion source gas

1-nebulizer gas (psig)50 60

Ion source gas2-turbo gas (psig)

30 40

Ion spray voltage (V) 5500 -4500Temperature (C) 750 750Probe X-axis

position (mm)15 15

Probe Y-axisposition (mm)

0 0



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intake is considerably lower than the Ontario provincialdrinking water quality standards of 5 mg/L for atrazineand its metabolites, and USEPA maximum contaminantlimit of 3 mg/L for atrazine in drinking water. Schottleret al. (1998) reported similar concentrations of atrazine(20–35 ng/L) in Lake Huron water. Since atrazine showsminimal degradation to volatilization, sorption and trans-formation in aquatic systems, atrazine concentration isexpected to be fairly consistent in the Great Lakes. TheGreat Lakes, having water residence times ranging from 3to 180 years and reported half-life of atrazine in LakeHuron water being more than 5 years, can transportatrazine to lower lake regions (Hua et al., 2006a).

Carbamazepine has been found to be quite persistent inthe aquatic environment. Earlier, Metcalfe et al. (2004)reported median concentration of carbamazpine to be 20ng/L in surface waters near wastewater treatment plantsdischarge. Hua et al. (2006b) observed 0.3 ng/L to 3.8 ng/Lof carbamazepine in a drinking water plant intake onDetroit river. Carbamazepine was detected in all samplesin this study at a mean concentration of about 29 ng/L inraw water. Fluoxetine was detected at a mean concentra-tion of 20 ng/L which is comparable to concentrationsreported by Kolpin et al. (2002) and Metcalfe et al.(2003b, 2004). Occurrence of atorvastatin in Canadian sur-face waters at a median concentration of 10 ng/L wasreported by Metcalfe et al. (2004). Atorvastatin was themost prescribed drug in the US in 2006 and 2007, and(Benotti et al., 2009) the most widely prescribed ‘‘statin’’class drug in Canada (Metcalfe et al., 2004). Atorvastatin

and ibuprofen were identified only during the August 2008sampling of this study at concentrations of 1.1 ng/L and17.2 ng/L, respectively.

Effect of Conventional Treatment Processes(Chemical Coagulation, Sedimentation andFiltration)

The coagulation process is mainly used for removingparticles and high molecular mass natural organic matter(NOM) during water treatment. Studies previously havereported minimal conversion (generally less than 25%)for most EDCs and PPCPs during conventional watertreatment processes (Ternes et al., 2002; Snyder et al.,2003; Westerhoff, 2003; Westerhoff et al., 2005; Jasimet al., 2006; Vieno et al., 2006; Snyder et al., 2007;Vieno et al., 2007). The current study likewise observedmarginal elimination of spiked EDCs and PPCPs in treat-ment Train 1 where PACl assisted coagulation followedby sand/anthracite filtration were employed. Spiking ofmicropollutants in raw water did not however, affectturbidity removal.

Figure 5 illustrates average concentrations of targetEDCs and PPCPs observed in Train 1 following coagula-tion, clarification and dual media (sand/anthracite) filtra-tion. From the decrease in concentration of the individualruns, fluoxetine was observed to achieve the highest meanremoval of about 12% only during conventional coagula-tion experiments in Train 1. Westerhoff et al. (2005) ear-lier observed 15% mean removals for fluoxetine duringcoagulation treatments in natural water. Other target com-pounds in the current study exhibited removal of less than10% during coagulation and sedimentation in Train 1demonstrating that the target micropollutants can easilyflout conventional water treatment processes.

Snyder et al. (2007) also reported less than 15% meanremoval for 34 of 36 target EDCs and PPCPs during coagula-tion treatment of four natural waters. The presence of NOM

4.23

.200

8

6.19

.200

8

8.20

.200

8

10.2

.200

8

10.9

.200

8

ATVIBU

FLXCBZ

ATZ

0

20

40

60

80

100

120

Concentr

ation (

ng/L

)ATV IBU FLX CBZ ATZ

FIGURE 4. Occurrence of EDCs and PPCPs in raw Lake Huron

water (abbreviations for compounds such as ATZ, CBZ, etc., are

explained in Table 6).

0.1

1

10

100

1000

IBU BPA NAP GEM DIC ATV ATZ CBZ FLX

Mean C

oncentr

ation (

ng/L

)

Spiked

Train 1 Clarifer

Train 1 Filter

FIGURE 5. Average concentrations of target compounds

observed following different treatment stages in Train 1. n ¼ 4 forTrain 1 clarified samples, and n ¼ 5 for spiked and Train 1 filtered

samples. Error bars indicate maximum and minimum concentrations.



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in natural water may affect the removal of EDCs and PPCPsdue to competition for coagulants. No significant improve-ments in target compounds eliminationwere observed follow-ing sand/anthracite dual media filtration. These results are inagreement with previous findings that EDCs and PPCPs, ingeneral, are not amenable to conventional treatmentprocesses(Westerhoff et al., 2005; Jasim et al., 2006; Snyder et al., 2007).

The hydrophilic nature of many EDCs and PPCPs oftenmake them resistant to the chemical coagulation process.Snyder et al. (2007) and Westerhoff et al. (2005) foundincreasing removal of micropollutants with increasing log-octanol water coefficient (log KOW), even for compoundsthat displayed lower removals (,10%) in their study. Suchtrends, however, could not be verified during the presentstudy (Figure 6). However, future experiments with anincreased number of target compounds would probably beable to address this issue.

Effect of Pre-Coagulation Advanced OxidationProcess

Ozonation and advanced oxidation processes (AOPs)have been reported to be extremely effective in removingmicropollutants. Advanced oxidation is particularly effi-cient for removing ozone recalcitrant compounds due tothe less preferential nature of the hydroxyl radicals(�OH). Typically �OH concentration in ozonation is low(10-12 M) (Snyder et al., 2006). The addition of H2O2 isan economic, fast and efficient process for increasing �OHconcentrations and thus it is the most widely used AOP indrinking water treatment (Von Gunten, 2003; Rosenfeldtet al., 2006; Snyder et al., 2006).

Figure 7 shows mean concentrations of the target EDCsand PPCPs observed in spiked, pre-coagulation AOP efflu-ent, subsequent clarifier and filtration unit samples fromtreatment Train 2. The applied oxidant doses (O3¼ 2.0–2.3mg/L and H2O2 ¼ 0.2 mg/L) in the current study achievedsubstantial removal of 6 of the 9 target EDCs and PPCPs.Following pre-coagulation AOP, bishphenol-A, naproxen,gemfibrozil, diclofenac and atorvastatin were reduced toconcentrations below the detection limit in most cases.Substantial removal (94%) was also observed for carbama-zepine, which was, however, consistently detected at a meanconcentration of 27 ng/L in Train 2 filtered water samples.

Figure 8 clearly shows that atrazine is the most recal-citrant of the target compounds, displaying only about22% mean removal following AOP. Ibuprofen also exhib-ited limited removal (41%) following pre-coagulationAOP. No significant increases in removal were observedfollowing subsequent coagulation and dual media filtra-tion treatment (Figure 7 and Figure 8). This clearly illus-trates that O3/H2O2 based AOP is responsible for high

0

5

10

15

0 1 2 3 4 5 6 7

log Kow

% R

em

oval in

Tra

in 1

Cla

rifier

FIGURE 6. Average percentage removals in Train 1 and log KOW

during coagulation experiments with polyaluminium chloride (PACl).

FIGURE 7. Mean concentrations of target compounds observed following different treatment stages in Train 2. When compounds were eithernot detected or detected at concentrations below the method detection limits (MDLs), a value of zero was assigned to calculate mean

concentrations. Error bars indicate maximum and minimum concentrations. N.D. – Not Detected. Sample detection Matrix: ni (X, Y, Z); na

denotes AOP effluent samples; nb denotes Train 2 clarifier samples; nc denotes Train 2 Filter samples. X (no of samples not detected); Y (no ofsamples detected below MDL but could not be quantified reliably); Z (total no. of samples).



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removal of target compounds. Average comparativeremovals of the target contaminants following filtrationin both trains are shown in Figure 9. Clearly, Train 2where pre-coagulation AOP coupled with conventionaltreatment processes were employed performed betterthan conventional treatment processes alone (Train 1).

The formation of �OH depends greatly on the watermatrix, especially the presence of NOM and alkalinity.Ozone decomposition is generally slow in waters withhigh alkalinity and low NOM (Acero and Von Gunten,2001; Huber et al., 2003). AOPs would particularly bevery efficient in removing ozone refractory compounds byaccelerating the ozone decomposition process in suchwater. However, during AOPs, disinfection benefits aregenerally curtailed due to the transient nature of �OH(Rosenfeldt et al., 2006; Snyder et al., 2006). The oxida-tion of micropollutants is greatly dependent on the sec-ond-order reaction rate constant with ozone ðKO3

Þ.Bisphenol A, diclofenac and carbamazepine display

high secondary reaction rate constants (KO3>105

M-1s-1) with ozone due to the presence of reactive phe-nol, aromatic amine and double bond respectively (Huberet al., 2003). Unlike molecular O3,

�OH displays highersecondary reaction rate constants for most organic com-pounds. Thus, higher removal of organic compounds isexpected when AOPs are employed. Atrazine due to its

lower secondary reaction rate constant with molecularozone (KO3

¼ 6 M-1s-1) generally displays lower removalduring ozonation. Previous studies have shown increasedremoval of atrazine (,62%) following AOPs (Westerhoffet al., 2005; Jasim et al. 2006; Snyder et al., 2006, 2007).

In the present study, the observed mean removal ofatrazine following pre-coagulation AOP was, however,

FIGURE 8. Mean removals of target EDCs and PPCPs in Train 1 and Train 2. C0 ¼ spiked concentration, C ¼ detected concentration. To

calculate % removal, a value of zero was assigned when compounds were not detected or when detected below the method detection limits

(MDL). Thus mean removal of 100% indicates that none of the samples had concentrations above MDLs.

FIGURE 9. Comparison of Train 1 and Train 2 overall removal

efficiencies. Error bars indicate maximum and minimum values(n ¼ 5). Points above the diagonal line (1:1) indicate that Train 2

was more efficient in removing target contaminants.



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much lower. Slow reacting pharmaceuticals, such as ibu-profen (KO3

¼ 9:6� 1 M-1s-1), are preferentially oxidizedby �OH during ozonation (Vieno et al., 2007). However, itis hard to presume their removal during ozonation as thewater matrix can greatly affect �OH formation potential.Snyder et al. (2007) achieved approximately 90% removalof ibuprofen with AOP (O3 ¼ 2.5 mg/L and H2O2 ¼ 0.5mg/L) after a contact time of 14 minutes. Average removalof ibuprofen observed during the current study followingAOP was about 41%. Since AOP was applied prior tocoagulation during the current study, it is presumed thata fraction of the applied dose was consumed by the initialozone demand of natural water (particles, NOM, UV254).

During a pilot-scale study of the ozonation of wastewater,Huber et al. (2005) found that turbidity can have considerableinfluence on the ozonation process. Thus, competition foroxidants with other impurities present in raw water mighthave contributed to the observed lower removals for atrazineand ibuprofen. Also, the low H2O2 to O3 ratio might haveaffected the conversionofO3and, thereby, theoverall removalof ozone recalcitrant contaminants. Higher oxidant dosesduring pre-coagulation AOPs or further oxidation followingsedimentation would probably achieve enhanced eliminationof these two compounds. Oxidant doses should be carefullychosen as higher oxidant doses during pre-coagulation AOPmay adversely impact subsequent coagulating treatment pro-cesses (Farvardin and Collins, 1989; Paode et al., 1995). Also,higher H2O2 to O3 ratios have been reported to increaseTHMs formation potential (Irabelli et al., 2008).

Thepresenceof suspended solids didnot seemtoaffect theremoval of carbamazepine, diclofenac, bisphenol-A, gemfi-brozil, atorvastatin and naproxen, during pre-coagulationAOP. This is in agreement with the finding of Huber et al.(2003), who noted that suspended solids would not inhibitthe removal of pharmaceuticals that react rapidly withmole-cular O3 (KO3

> 105 M-1s-1). High to complete conversionfollowing ozonation have been observed for these com-pounds in other earlier studies. Fluoxetine has beenshown to achieve excellent removal (.91%) from waterfollowing ozonation and O3/H2O2 based AOP(Westerhoff et al., 2005; Snyder et al., 2007).

In the current study 58% of fluoxetine removal wasachieved following AOP. The removal of fluoxetine how-ever, increased to over 80% following subsequent clarifica-tion and filtration processes. Reasons behind such increasein removal following the coagulation process could not beexplained. The specific effects of various water quality para-meters and treatment parameters on the removal of targetEDCs and PPCPs were not evaluated during this study. Atthe doses applied during water treatment, AOPs would notmineralize contaminants, butwould instead form intermedi-ate or by-products (VonGunten, 2003). By-products forma-tion and subsequent structural modifications were beyondthe scope of the current study.

CONCLUSIONS

The occurrence and removal of nine EDCs and PPCPsfrom Lake Huron water were studied. Atrazine, carbamaze-pine, fluoxetine were detected in at least four samples of rawLake Huron water at trace concentrations (,58 ng/L) andibuprofen and atorvastatin were detected in only one sample.Thus, 6of the 9 target compoundswerenotdetected inat leastfour raw water samples. The presence of atrazine in LakeHuron water has significant implications as the water cantransport and contaminate drinking water sources in thedownstream areas. The occurrence of these compounds how-ever, does not necessarily confirmhealth risk andneither doesnon-detection guarantee safety. As a consequence, the deter-mination of toxicological relevance is important (Snyderet al., 2007). Raw water for the study was collected from asingle location on Lake Huron and therefore, the results ofthe occurrencemay not apply to other areas of the lake. Also,the sampling period of the study covered approximately 8months in the year. Therefore, the study did not providesufficient basis to discuss seasonal variation of occurrence ofthe target compounds in the source water.

Pilot-scale investigations involving coagulation withPACl and dual media filtration did not exhibit any signifi-cant removal of the target contaminants. On the otherhand, O3/H2O2 based AOP in conjunction to coagulation,sedimentation and filtration attained high removal of themajority of the target EDCs and PPCPs. Overall, treatmentTrain 2 of the pilot plant was found to be very efficient inremoving spiked EDCs and PPCPs, as 5 of 9 compoundswere not detected in filtered water. The results show thatO3/H2O2 based pre-coagulation AOP have a great potentialfor the treatment of trace contamination of pharmaceuti-cals in the Great Lakes region. Pre-coagulation AOPapplied during the study however, failed to achieve signifi-cant removal of atrazine and ibuprofen. Also, trace levelresiduals of carbamazepine and fluoxetine were still detect-able following filtration in Train 2. By-products of certaincompounds may be of health concern and future researchshould be directed to identify the degradation products ofAOPs and their toxicological relevance.

In general, the human health risks from the presence oftrace concentrations of PPCPs in drinkingwater appear to below (Webb et al., 2003). However, the effects of chronic andsynergistic exposure to such compounds are yet to be eluci-dated. Limited number of Canadian drinking water treat-ment plants use advanced treatment technologies such asozonation orAOPs (Metcalfe et al., 2004). The risk of gettingunwillingly medicated via drinking water may be an issue forthose communities whose source water contains EDCs andPPCPs.Needless to say further research iswarranted to studythe Great Lakes to identify the extent of PPCPs and EDCsoccurrence in thosewater bodies and tomaximize removal ofcontaminants during drinking water treatment.



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As the science of analytical chemistry progresses, morechemicals at trace level would be detected and no singletreatmentwould possibly be able to provide total safeguardagainst all contaminants. Thus amultiple barrier approachmay be necessary to ensure acceptable finished water qual-ity chemically and microbiologically. It is probably pru-dent that drinkingwater treatment utilities consider the useof advanced water treatment technologies if the removal ofemerging contaminants is considered in future plantupgrades. Advance treatment techniques will require sig-nificant capital investment and increase operational costsand hence careful considerations should be made to justifysuch installation.

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